Method of forming high-k dielectric films based on novel titanium, zirconium, and hafnium precursors and their use for semiconductor manufacturing

ABSTRACT

A method of forming on at least one support at least one metal containing dielectric films having the formula (M 1   1-a  M 2   a ) O b  N c , wherein: 0≦a&lt;1, 01 and M 2  being metals Hf, Zr or Ti using precursors with pentadienyl ligands and/or cyclopentadienyl ligands.

The invention relates to a method of forming high-k dielectric filmssuch as hafnium or zirconium oxides or oxynitrides and their use formanufacturing semi-conductors.

BACKGROUND

With the shrink of the critical dimensions of the future generation ofsemi-conductor devices, the introduction of new materials, especiallyhaving high dielectric constant, is required. In CMOS architectures,high-k dielectrics are required to replace SiO₂ which reaches itsphysical limits, having typically a SiO₂ equivalent thickness of about 1nm.

Similarly, high-k dielectrics are required in Metal-Insulator-Metalarchitectures for RAM applications. Various metal compositions have beenconsidered to fulfill both the materials requirements (dielectricconstant, leakage current, crystallisation temperature, charge trapping)and the integration requirements (thermal stability at the interface,dry etching feasibility . . . ).

The Group IV based materials, such as HfO₂, HfSiO₄, ZrO₂, ZrSiO₄,HfZrO₄, HfLnO_(x) (Ln being selected from the group comprising scandium,yttrium and rare-earth elements) are among most promising materials.Furthermore, Group IV metals composition can also be considered forelectrode and/or Cu diffusion barrier applications, such as TiN formid-gap metal gate and MIM RAM, HfN, ZrN, HfSi, ZrSi, HfSiN, ZrSiN,TiSiN . . . .

Deposition processes of such thin films with reasonable throughput andacceptable purity are vapor phase deposition techniques, such as MOCVD(Metal-organic Chemical Vapor Deposition) or ALD (Atomic LayerDeposition). Such deposition processes require metal precursors thatmust fulfill drastic requirements for a proper industrial use.

It is known from Kim et al., Electrochem Soc Proceedings 2005-05, 397,2005, to use HfCl₄ for the deposition of HfO₂ by ALD. However, someby-products generated during the deposition process, such as HCl or Cl₂,can cause surface/interface roughness that can be detrimental to thefinal properties. Other possible byproducts, depending on the oxygensource used, may be hazardous. For instance, OCl₂, through the OClfragment by QMS, has been detected as a byproduct of the reactionbetween HfCl₄ and O₃. Moreover, in the case of high-k oxide, Cl or Fimpurities are detrimental to the final electrical properties and Cl andF-containing precursors are therefore not preferred.

Triyoso et al. in J. Electrochem. Soc. 152 (3) G203-G209 (2005), Changet al. in Electrochem. Solid. State Let., 7 (6) F42-F44 (2004), studiedthe use of Hf(OtBu)₄ for HfO₂ MOCVD and ALD, respectively. Williams etal. have evaluated Hf(mmp)₄ and Hf(OtBu)₂(mmp)₂ for MOCVD of HfO₂. InWO2003035926, Jones et al. disclose solid Ti, Hf, Zr and La precursorsimproved with donor functionalized alkoxy ligand(1-methoxy-2-methyl-2-propanolate[OCMe₂CH₂OMe, mmp]) which helpsinhibiting oligomerisation of Zr and Hf alkoxide compounds andincreasing their stability towards moisture. However, all those alkoxideprecursors have the drawback not to enable self-limited deposition inALD process.

Alkylamides precursors such as Hf(NEtMe)₄, Hf(NMe₂)₄, Hf(NEt₂)₄ . . .have been widely disclosed in the literature such as by Senzaki et al inJ. Vac. Sci. Technol. A 22(4) July/August 2004, Haussmann et al. inChem. Mater. 2002, 14, 4350-4353, Kawahara et al. in J. Appl. Phys., Vol43, N°7A, 2004, pp 4129-4134, Hideaki et al. in JP2002093804, Metzner etal. in U.S. Pat. No. 6,858,547, Dip et al. in US20050056219. Group IValkylamides are both suitable for ALD and MOCVD processes. Furthermore,some are liquid at room temperature (TDEAH and TEMAH) and of sufficientvolatility, and they allow self-limited ALD at low temperature for alimited thermal budget process. However, Group IV alkylamides haveseveral drawbacks:

-   -   they may decompose during the distribution to some extent        leading to a possible clogging of the feeding line or the        vaporizer,    -   they may generate particles during deposition,    -   they may entail non-uniform compositions during deep trenches        deposition processes,    -   they only allow a narrow self-limited ALD temperature window,        hence reducing the process window.

Carta et al. disclose in Electrochem Soc Proceedings, 260, 2005-09, 2005the use of bis(cyclopentadienyl)bisdimethyl hafnium and several authors(Codato et al., Chem Vapor Deposition, 159, 5, 1995; Putkonen et al., JMater Chem, 3141, 11, 2001; Niinisto et al., Langmuir, 7321, 21, 2005)disclose the use of bis(cyclopentadienyl)bisdimethyl zirconium, whichallow an efficient ALD deposition process with an ALD window up to 400°C. and an achievement of films with less than 0.2% C in optimizedconditions with H₂O as co-reactant. However, HfCp₂Me₂ and ZrCp₂Me₂ bothhave the drawback of being solid products at room temperature (HfCp₂Me₂melting point is 57.5° C.). This makes inconvenient their use by ICmakers.

In U.S. Pat. No. 6,743,473, Parkhe et al. disclose the use of(Cp(R)_(n))_(x)MH_(y-x), to make a metal and/or a metal nitride layer,where M is selected from tantalum, vanadium, niobium and hafnium, Cp iscyclopentadienyl, R is an organic group. Only examples of tantalum andniobium cyclopentadienyl compounds are disclosed. However, no liquidprecursor or a precursor having a melting point lower than 50° C. isdisclosed.

Today, there is a need for providing liquid or low melting point (<50°C.) group IV precursor compounds, and in particular Hf and Zr compounds,that would allow simultaneously:

-   -   proper distribution (physical state, thermal stability at        distribution temperatures),    -   wide self-limited ALD window,    -   deposition of pure films either by ALD or MOCVD.

DISCLOSURE

According to the invention, certain cyclopentadienyl or pentadienylbased group IV metal-organic precursors have been found suitable for thedeposition of Group IV metal containing thin films by either ALD orMOCVD processes and have the following advantages:

-   -   They are liquid at room temperature or having a melting point        lower than 50° C.,    -   They are thermally stable to enable proper distribution (gas        phase or direct liquid injection) without particles generation,    -   They are thermally stable to allow wide self-limited ALD        window, 4) allowing deposition of a variety of Group IV metals        containing films, including ternary or quaternary materials, by        using one or a combination of co-reactants (selected from the        group comprising of H₂, NH₃, O₂, H₂O, O₃, SiH₄, Si₂H₆, Si₃H₈,        TriDMAS, BDMAS, BDEAS, TDEAS, TDMAS, TEMAS, (SiH₃)₃N, (SiH₃)₂O,        TMA or an aluminum-containing precursor, TBTDET, TAT-DMAE, PET,        TBTDEN, PEN, lanthanide-containing precursors such as Ln(tmhd)₃        . . . ).

According to the invention, there is provided a method of forming on atleast one substrate at least one metal containing dielectric film havingthe formula (M¹ _(1-a) M² _(a)) O_(b) N_(c), wherein:

-   -   0≦a<1    -   0<b≦3, preferably 1.5≦b≦2.5    -   0≦c≦1, preferably 0≦c≦0.5    -   M¹ and M² being metals

said method comprising the steps of:

-   -   (a) providing a substrate into a reactor    -   (b) introducing into said reactor at least one metal containing        precursor having the formula:

(R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z)

wherein:

-   -   M¹=Hf, Zr and/or Ti;    -   (R_(y)Op) represents one pentadienyl (Op) ligand, substituted or        not, with y R substituents in any position on Op;    -   (R_(t)Cp) represents one cyclopentadienyl (Cp) ligand,        substituted or not with t R substituants in any position on Cp;    -   Each R substituting a pentadienyl or each R substituting a        cyclopentadienyl is a ligand independently selected from the        group consisting of Cl, C1-C4 linear or branched, alkyl,        alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl,        each R being similar to or different from other R substituting        the pentadienyl and other R substituting the cyclopentadienyl;    -   Each R′ is a ligand independently selected from the group        consisting of H, Cl, C1-C4 linear or branched, alkyl,        alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl,        each R′ being similar or different.    -   x is an integer representing the number of pentadienyl ligands,        substituted or not;    -   z is an integer representing the number of cyclopentadienyl        ligands, substituted or not;    -   y is an integer representing the number of substituants on each        Op, and is independent selected for each Op;    -   t is an integer representing the number of substituants on each        Cp, and is independent selected for each Cp;    -   0≦x≦3, preferably x=0 or 1;    -   0≦z≦3, preferably z=2;    -   0≦y≦7, preferably y=2 and in this case each R is a methyl group;    -   0≦t≦5, preferably t=1 and R is a methyl group;    -   Unspecified substituents to Cp or Op ligands are H by default.    -   (c) optionally introducing at least one M² containing precursor,        M² being selected from the group essentially consisting of Mg,        Ca, Zn, B, Al, In, Lanthanides (Sc, Y, La and rare earths), Si,        Ge, Sn, Ti, Zr, Hf, V, Nb, Ta;    -   (d) providing at least one oxygen containing and/or nitrogen        containing fluid into said reactor;    -   (e) reacting said at least one metal containing precursor with        said at least one oxygen containing and/or nitrogen containing        fluid;    -   (f) depositing said (M¹ _(1-a) M²a) O_(b) N_(c), film onto said        substrate at a temperature comprised between 100° C. to 500° C.,        preferably between 150° C. and 350° C.,        provided that when a=0, b=2, c=0, x=0, z=2, at least one t on at        least one Cp is different from zero.

The oxygen containing fluids shall be preferably selected from the groupconsisting of O₂, O₃, H₂O, H₂O₂, oxygen-containing radicals such as O.or OH. and mixtures thereof, while the nitrogen-containing fluids shallbe selected from the group consisting of N₂, NH₃, hydrazine and itsalkyl or aryl derivatives, nitrogen-containing radicals such as N., NH.,NH₂. and mixtures thereof.

According to one embodiment when both nitrogen and oxygen are needed,the oxygen and nitrogen-containing fluids may be selected from the groupconsisting of NO, NO₂, N₂O, N₂O₅, N₂O₄ and mixtures thereof, (selectingone of those fluids automatically generate an oxynitride layer, with acertain ration of N/O molecules. If the certain ratio is notappropriate, then another nitrogen containing fluid and/or anotheroxygen containing fluid is needed.

To carry out the process of the invention, the pressure shall becomprised between 1 Pa and 100000 Pa, preferably between 25 Pa and 1000Pa.

The various reactants can be introduced into the reactor eithersimultaneously (chemical vapor deposition), sequentially (atomic layerdeposition) or different combinations thereof (one example is tointroduce e.g. the two metal sources together in one pulse and theoxygen gas in a separate pulse (modified atomic layer deposition);another example is to introduce oxygen continuously and to introducemetal source by pulse (pulsed chemical vapor deposition)).

According to another embodiment the method according to the inventionmay further comprise the step of (g) providing at least one metalcontaining precursor containing at least one of the followingprecursors: M¹(NMe₂)₄, M¹(NEt₂)₄, M¹(NMeEt)₄, M¹(mmp)₄, M¹(OtBu)₄,M¹(OtBu)₂(mmp)₂ and mixtures thereof.

Preferably, the at least one metal containing precursor introduced instep b) defined here above shall have a melting point below 50° C.,preferably below 35° C. while more preferably the at least one metalcontaining precursor shall be liquid at room temperature.

The method according to the invention may also further comprises thestep of:

-   -   (h) mixing together at least two different metal containing        precursors A and B to provide a precursor mixture, A being        (R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z) and B being selected from        the group consisting of (R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z),        M¹(NMe₂)₄, M¹(NEt₂)₄, M¹(NMeEt)₄, M¹(mmp)₄, M¹(OtBu)₄,        M¹(OtBu)₂(mmp)₂ and mixtures thereof, and    -   (i) providing said metal precursor mixture into said reactor.

According to an alternative method of the invention, step (h) and (i) asdefined above are carried out instead of step (b).

According to another embodiment of the invention, to form an M¹oxydecontaining film wherein a=0, b being equal to about 2 and c=0, the metalcontaining precursor of steps (b) and/or (h) is selected from the groupconsisting of: HfCp₂Cl₂, Hf(MeCp)₂Me₂, HfCp(MeCp)Cl₂, Hf(MeCp)₂Cl₂,HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂,ZrCP₂Cl₂, Zr(MeCp)₂Me₂, ZrCp(MeCp)Cl₂, Zr(MeCp)₂Cl₂, ZrCp(MeCp)Me₂,Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂ and mixtures thereof.

According to still another embodiment of the invention, to form anM¹oxynitride-containing dielectric film wherein a=0, 1.5≦b≦2.5 and0<c≦0.5, the metal containing precursor of step (b) and/or (h) shall beselected from the group consisting of HfCP₂Cl₂, Hf(MeCp)₂Me₂,HfCp(MeCp)Cl₂, Hf(MeCp)₂Cl₂, HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂,Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂, ZrCP₂Cl₂, Zr(MeCp)₂Me₂, Zr(MeCp)₂Cl₂,ZrCp(MeCp)Me₂, Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂ andmixture thereof.

According to another embodiment of the invention to form an M¹M² Oxidecontaining dielectric film wherein 0≦a<1 and c=0, the metal containingprecursor of step (b) and/or (h) shall be selected from the groupconsisting of HfCP₂Cl₂, Hf(MeCp)₂Me₂, HfCp(MeCp)Cl₂, Hf(MeCp)₂Cl₂,HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂,ZrCP₂Cl₂, Zr(MeCp)₂Me₂, ZrCp(MeCp)Cl₂, Zr(MeCp)₂Cl₂, ZrCp(MeCp)Me₂,Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂, the M² containingprecursor of step (c) being introduced into the reactor, said precursorbeing preferably selected from the group consisting of Si, Mg,lanthanides (i.e. Sc, Y and rare earths) and/or Ta.

According to another different embodiment of the invention, the M²containing precursor is selected from the group consisting ofdisiloxane, trisilylamine, disilane, trisilane, a alkoxysilaneSiH_(x)(OR¹)_(4-x), silanol Si(OH)_(x)(OR¹)_(4-x)(preferablySi(OH)(OR¹)₃; more preferably Si(OH)(OtBu)₃), aminosilaneSiH_(x)(NR¹R²)_(4-x) (where x is comprised between 0 and 4; R¹ and R²are independently H or a C1-C6 carbon chain, either linear, branched orcyclic; preferably TriDMAS SiH(NMe₂)₃; BTBAS SiH₂(NHtBu)₂); BDEASSiH₂(NEt₂)₂) and mixtures thereof (or their germanium equivalents),trimethylaluminum, dimethylaluminum hydride, alkoxyalane AlR^(i)_(x)(OR′)_(3-x) (where x is comprised between 0 and 4; each R^(i) isindependently H or a C1-C6 carbon chain, either linear, branched orcyclic; preferably AlR¹R²(OR′), with R¹ and R² are independently H or aC1-C6 carbon chain, either linear, branched or cyclic, most preferablyAlMe₂(OiPr)), amidoalane AlR^(i) _(x)(NR′R″)_(3-x) (where x is comprisedbetween 0 and 3; each R^(i) is independently H or a C1-C6 carbon chain,either linear, branched or cyclic), Ta(OMe)₅, Ta(OEt)₅,Ta(OR¹)₄(O—C(R²)(R³)—CH₂—OR⁴) (each R^(i) is independently H or a C1-C6carbon chain, either linear, branched or cyclic, preferably TAT-DMAETa(OEt)(OCMe₂CH₂—OMe)), Ta(OR¹)₄(O—C(R²)(R³)—CH₂—N(R⁴)(R⁵)) (each R^(i)is independently H or a C1-C6 carbon chain, either linear, branched orcyclic, Ta(NMe₂)₅, Ta(NEt₂)₄, Ta(NEt₂)₅, Ta(═NR¹)(NR²R³)₃ (each R¹, R²and R³ are independently H or a C1-C6 carbon chain, either linear,branched or cyclic and where the amino ligand can have differentsubstituant), Nb(OMe)₅, Nb(OEt)₅, Nb(OR¹)₄(O—C(R²)(R³)—CH₂—OR⁴) (eachR^(i) is independently H or a C1-C6 carbon chain, either linear,branched or cyclic, preferably NBT-DMAE Nb(OEt)(OCMe₂CH₂—OMe)),Nb(OR¹)₄(O—C(R²)(R³)—CH₂—N(R⁴)(R⁵)) (each R¹ is independently H or aC1-C6 carbon chain, either linear, branched or cyclic, Nb(NMe₂)₅,Nb(NEt₂)₄, Nb(NEt₂)₅, Nb(═NR¹)(NR²R³)₃ (each R¹, R² and R³ areindependently H or a C1-C6 carbon chain, either linear, branched orcyclic and where the amino ligand can have different substituent), alanthanide metal source (Sc, Y, La, Ce, Pr, Nd, Gd . . . ), a sourcewith at least one β-diketonate ligand, such as having the form ofLn(—O—C(R¹)—C(R²)—C(R³)—O—)(—O—C(R⁴)—C(R⁵)—C(R⁶)—O—)(—O—C(R⁷)—C(R⁸)—C(R⁹)—O—)where each R^(i) is independently H or a C1-C6 carbon chain, eitherlinear, branched or cyclic), or of the form of a cyclopentadienyllanthanide Ln(R¹Cp)(R²Cp)(R³CP) (where each R^(i) is independently H ora C1-C6 carbon chain, either linear, branched or cyclic),Ln(NR¹R²)(NR³R⁴)(NR⁵R⁶) (where each R^(i) is bonded to nitrogen and isindependently H or a C1-C6 carbon chain, either linear, branched orcyclic or an alkylsilyl chain of the form SiR⁷R⁸R⁹ where each R^(i) isbonded to silicon and is independently H or a C1-C4 carbon chain, eitherlinear, branched or cyclic), a divalent metal A (preferably Mg, Ca, Zn)of the form A(—O—C(R¹)—C(R²)—C(R³)—O—)(—O—C(R⁴)—C(R⁵)—C(R⁶)—O—) (whereeach R^(i) is independently H or a C1-C6 carbon chain, either linear,branched or cyclic) or of the form of a cyclopentadienyl lanthanideA(R¹Cp)(R²Cp) (where each R^(i) is independently H or a C1-C6 carbonchain, either linear, branched or cyclic).

According to an embodiment of the invention, to form an M¹M² oxynitridecontaining dielectric film wherein 0≦a<1 and 0<c≦0.5, the metalcontaining precursor of step (b) and/or (h) shall be selected from thegroup consisting of HfCP₂Cl₂, Hf(MeCp)₂Me₂, HfCp(MeCp)Cl₂, Hf(MeCp)₂Cl₂,HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂,ZrCP₂Cl₂, Zr(MeCp)₂Me₂, ZrCp(MeCp)Cl₂, Zr(MeCp)₂Cl₂, ZrCp(MeCp)Me₂,Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂, the M² containingprecursor of step (c) being introduced into the reactor, said M²precursor being preferably selected from the group consisting of Si, Mg,lanthanides (i.e. Sc, Y and rare earths) and/or Ta, and wherein in step(d) at least one oxygen containing precursor and at least one nitrogencontaining precursor is introduced into the reactor.

Preferably, when M¹M² oxynitride are deposited, the M² containingprecursor is selected from the group consisting of disiloxane,trisilylamine, disilane, trisilane, a alkoxysilane SiH_(x)(OR¹)_(4-x), asilanol Si(OH)_(x)(OR¹)_(4-x) (preferably Si(OH)(OR¹)₃, more preferablySi(OH)(OtBu)₃ an aminosilane SiH_(x)(NR¹R²)_(4-x) (where x is comprisedbetween 0 and 4; R¹ and R² are independently H or a C1-C6 carbon chain,either linear, branched or cyclic; preferably TriDMAS SiH(NMe₂)₃, BTBASSiH₂(NHtBu)₂); BDEAS SiH₂(NEt₂)₂) and mixtures thereof (or theirgermanium equivalents), trimethylaluminum, dimethylaluminum hydride, analkoxyalane AlR^(i) _(x)(OR′)_(3-x) (where x is comprised between 0 and4; R¹ and R² are independently H or a C1-C6 carbon chain, either linear,branched or cyclic; preferably AlR¹R²(OR′), most preferablyAlMe₂(OiPr)), an amidoalane AlR^(i) _(x)(NR′R″)_(3-x) (where x iscomprised between 0 and 4; R¹ and R² are independently H or a C1-C6carbon chain, either linear, branched or cyclic), Ta(OMe)₅, Ta(OEt)₅,Ta(OR¹)₄(O—C(R²)(R³)—CH₂—OR⁴) (each R^(i) is independently H or a C1-C6carbon chain, either linear, branched or cyclic, preferably TAT-DMAETa(OEt)(OCMe₂CH₂—OMe)), Ta(OR¹)₄(O—C(R²)(R³)—CH₂—N(R⁴)(R⁵)) (each R^(i)is independently H or a C1-C6 carbon chain, either linear, branched orcyclic, Ta(NMe₂)₅, Ta(NEt₂)₄, Ta(NEt₂)₅, Ta(═NR¹)(NR²R³)₃ (each R¹ andR² are independently H or a C1-C6 carbon chain, either linear, branchedor cyclic and where the amino ligand can have different substituant),Nb(OMe)₅, Nb(OEt)₅, Nb(OR¹)₄(O—C(R²)(R³)—CH₂—OR⁴) (each R′ isindependently H or a C1-C6 carbon chain, either linear, branched orcyclic, preferably NBT-DMAE Nb(OEt)(OCMe₂CH₂—OMe)),Nb(OR¹)₄(O—C(R²)(R³)—CH₂—N(R⁴)(R⁵)) (each R^(i) is independently H or aC1-C6 carbon chain, either linear, branched or cyclic, Nb(NMe₂)₅,Nb(NEt₂)₄, Nb(NEt₂)₅, Nb(═NR¹)(NR²R³)₃ (each R¹, R² and R³ areindependently H or a C1-C6 carbon chain, either linear, branched orcyclic and where the amino ligand can have different substituant), alanthanide metal source (Sc, Y, La, Ce, Pr, Nd, Gd . . . ) source withat least one β-diketonate ligand, such as of the formLn(—O—C(R¹)—C(R²)—C(R³)—O—)(—O—C(R⁴)—C(R⁵)—C(R⁶)—O—)(—O—C(R⁷)—C(R⁸)—C(R⁹)—O—)where each R^(i) is independently H or a C1-C6 carbon chain, eitherlinear, branched or cyclic), or of the form of a cyclopentadienyllanthanide Ln(R¹Cp)(R²Cp)(R³CP) (where each R^(i) is independently H ora C1-C6 carbon chain, either linear, branched or cyclic),Ln(NR¹R²)(NR³R⁴)(NR⁵R⁶) (where each R^(i) is bonded to nitrogen and isindependently H or a C1-C6 carbon chain, either linear, branched orcyclic or an alkylsilyl chain of the form SiR⁷R⁸R⁹ where each R^(i) isbonded to silicon and is independently H or a C1-C4 carbon chain, eitherlinear, branched or cyclic), a divalent metal A (preferably Mg, Ca, Zn)of the form A(—O—C(R¹)—C(R²)—C(R³)—O—)(—O—C(R⁴)—C(R⁵)—C(R⁶)—O—) (whereeach R^(i) is independently H or a C1-C6 carbon chain, either linear,branched or cyclic) or of the form of a cyclopentadienyl lanthanideA(R¹Cp)(R²Cp) (where each R^(i) is independently H or a C1-C6 carbonchain, either linear, branched or cyclic).

The invention also may generally relates to the use of(R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z) to make dielectric films e.g. forintegrated circuits or Metal Insulator Metal (MIM) architectures forRandom Access Memories.

According to still another aspect, the invention relates also to newprecursors comprising composition for semi-conductor or RAM manufacture,said precursor having the formula:

(R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z)

wherein

-   -   M¹=Hf, Zr and/or Ti    -   (R_(y)Op) represents one pentadienyl (Op) ligand, substituted or        not, with y R substituants in any position on Op;    -   (R_(t)Cp) represents one cyclopentadienyl (Cp) ligand,        substituted or not, with t R substituants in any position on Cp;    -   Each R substituting a pentadienyl or R substituting a        cyclopentadienyl are organics independently selected from the        group consisting of Cl, C1-C4 linear or branched, alkyl,        alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl,        each R_(y) or each R_(t) being similar to or different from        other R_(y) or other R_(t), respectively;    -   Each R′ is an organics independently selected from the group        consisting of H, Cl, C1-C4 linear or branched, alkyl,        alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl,        each R′ being similar or different.    -   x is an integer representing the number of pentadienyl ligand,        substituted or not    -   z is an integer representing the number of cyclopentadienyl        ligand, substituted or not;    -   y is an integer representing the number of substituants on each        Op, and is independent by selected for each Op;    -   t is an integer representing the number of substituants on each        Cp, and is independent selected for each Cp;    -   0≦x≦3, preferably x=0 or 1;    -   0≦z≦3, preferably z=2;    -   0≦y≦7, preferably y=2 and in this case each R is methyl;    -   0≦t≦5, preferably t=1 and R is a methyl group;    -   Unspecified substituents to Cp or Op ligands are H by default;    -   All R′ are not simultaneously equal to H when x=0,        provided that when a=0, b=2, c=0, x=0, z=2, at least one t on at        least one Cp is different from 0.

According to another embodiment, such new precursor composition mayfurther comprise a second metal containing precursor, different from thefirst metal precursor, said second metal containing precursor beingselected from the group consisting of(R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z), M¹(NMe₂)₄, M¹(NEt₂)₄,M¹(NEtMe)₄, M¹(mmp)₄, M¹(OtBu)₄, M¹ (OtBu)₂(mmp)₂ and mixtures thereof.

DETAILED DESCRIPTION Example I Deposition of Metal Oxide Film M¹O₂ withM¹ being Preferably Hafnium and Zirconium

The film to be deposited relates to the case where a=0, b is about 2 andc=0.

To make the deposition of such film on the surface of a wafer or in adeep trench to manufacture MIM structures for DRAM, one need to vaporizethe M¹ metal source as defined in steps (b) and/or (h) here above intothe reactor (preferably Hafnium or Zirconium), inject an oxygen source,preferably moisture, oxygen or ozone into said reactor, react theproducts at appropriate temperature (preferably between 150° C. and 350°C.) and pressure (preferably between 25 Pa and 1000 Pa) for the durationnecessary to achieve either a thin film deposition on the substrate orto fill out deep trenches by ALD or pulse CVD process (sequential pulseinjection of metal sources are necessary in order to allow regulardeposition of the oxide in the trench to progressively fill out thistrench and provide no voids in the dielectric film and therefore nodefect in the capacitor dielectric film).

The dielectric film shall have the desired final composition (hereessentially variations of the b value around 2 modifying the ratio ofprecursor to oxygen source).

It is possible to select the M¹ containing precursors from the threefollowing options, a, b or c:

a) M¹ source is a molecule or a mixture of molecules having the formula(R_(t)Cp)_(z)M¹R′_(4-z), wherein:

-   -   M¹ is a group IV metal selected from the group consisting of Hf,        Zr, Ti or mixture thereof.    -   z is an integer comprised between 1 and 3, preferably z=2.    -   t is an integer between 0 and 5, preferably t=1.    -   Cp is a cyclopentadienyl ligand. Each Cp comprises t        substituents R    -   Each R substituting a cyclopentadienyl is a ligand independently        selected from the group consisting of C1, C1-C4 linear or        branched, alkyl, alkylamides, alkoxide, alkylsilylamides,        amidinates, carbonyl, isonitrile, each R being similar to or        different from other R substituting the cyclopentadienyl;    -   Each R′ is a ligand independently selected from the group        consisting of H, Cl, C1-C4 linear or branched, alkyl,        alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl,        each R′ being similar or different from other R′.    -   When one or several Cp ligands are present in the molecule, the        number of substituents on each Cp can be different, their        substituents (R) can be different and in whatever position on        each Cp.

The preferred molecule is M(RCp)₂Me₂. More preferably R is Me or Et,while the molecule is preferably selected from the group of moleculeshaving melting point lower than 35° C., more preferably which is liquidor which can be easy liquefied for easy delivery.

-   -   Delivery of molecules in liquid form is usually carried out by        bubbling an inert gas (N₂, He, Ar, . . . ) into the liquid and        providing the inert gas plus liquid gas mixture to the reactor.    -   The formula of the molecule is shown below:

b) The M¹ metal source is a molecule or mixture of molecules having thegeneral formula: (R_(y)Op)_(x) M¹R′_(4-x), wherein:

-   -   M¹ is a group IV metal (Hf, Zr, Ti).    -   x is an integer comprised between 1 and 3, preferably, x=2.    -   y is an integer between 1 and 7. Preferentially y=2.    -   Op is a pentadienyl ligand. Each Op comprises y substituents R.    -   R and R′ are organic ligand independently selected from the        group consisting of H, Cl, C1-C4 linear or branched, alkyl,        alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl,        isonitrile. If several Op ligands are present in the molecule,        the number of substituents can be similar or different, their        substituents (R) can be different and in whatever position. Each        R substituting a pentadienyl may be similar or different from        other R also substituting a pentadienyl, either the same or a        different one. Each R′ may be similar or different from other        R′. Each Op may comprise one or several R.    -   The molecule is preferably M¹(2,4-R₂OP)₂Me₂. More preferably R        is Me (i.e. metal dimethyl bis(2,4-dimethylpentadienyl).    -   The molecule has a melting point lower than 50° C. The molecule        has preferably a melting point lower than 35° C., i.e. which is        liquid or can be easy liquefied for easy delivery.

The general formula of the molecule is:

with one or several (y times) R on each Op cycle.c) The M¹ metal source is a molecule or mixture of molecules having thegeneral formula: (R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z), wherein:

-   -   M¹ is a group IV metal (Hf, Zr, Ti).    -   x and z are integers comprised between 1 and 3, preferably x=1,        and z=1.    -   y and t are integers between 1 and 7, preferably y=2 and t=1.    -   Cp is a cyclopentadienyl ligand. Each Cp comprises t        substituents R.    -   Op is a pentadienyl ligand. Each Op comprises y substituents R.    -   Each R substituting a pentadienyl and each R substituting a        cyclopentadienyl, and R′ are ligands independently selected from        the group consisting of H, C1, C1-C4 linear or branched, alkyl,        alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl,        isonitrile. Each R substituting a pentadienyl may be similar or        different from other R substituting a pentadienyl, (either on        the same or on a different one), or a cyclopentadienyl. Each R        substituting a cyclopentadienyl may be similar or different from        other R substituting a cyclopentadienyl, (either the same or on        a different one), or a pentadienyl. Each Op and/or Cp may have        one or several R substituents. If several Op ligands are present        in the molecule, the number of substituents can be similar or        different, their substituents (R) can be different. The same        applies for the substituents R on Cp.    -   The molecule is preferably M(RCp)(2,4-R₂Op)Me₂. More preferably        R substituting the cyclopentadienyl and the R's substituting the        pentadienyl are Me (i.e. metal        dimethyl(2,4-dimethylpentadienyl)(methylcylopentadienyl)).    -   The molecule has preferably a melting point lower than 35° C.,        i.e. which is liquid or can be easy liquefied for easy delivery.

The general formula of the molecule is:

The oxygen source shall be preferably, without limitations, oxygen (O₂),oxygen radicals (for instance O. or OH.), such as radicals generated bya remote plasma system, ozone, NO, N₂O, NO₂, moisture (H₂O) and H₂O₂.

Regarding the deposition process by itself, the reactants can beintroduced into the reactor simultaneously (chemical vapor deposition),sequentially (atomic layer deposition) or different combinations (oneexample is to introduce metal source and the other metal source togetherin one pulse and oxygen in a separate pulse [modified atomic layerdeposition]; another option is to introduce oxygen continuously and/orto introduce the metal source by pulse (pulsed-chemical vapordeposition).

Example II Deposition of Metal Oxynitride Films M¹ON with M¹ beingPreferably Hafnium and Zirconium

The film deposited relates to the case where a=0 and b and c aredifferent from zero.

All the information given in Example I is applicable in this Example II,except that nitrogen needs to be introduced into the reactor.

The nitrogen shall be selected from a nitrogen source selected from thegroup comprising nitrogen (N₂), ammonia, hydrazine and alkylderivatives, N-containing radicals (for instance N., NH., NH₂.), NO,N₂O, NO₂ or the like.

Example III Deposition of M¹M² Metal Oxide Films with M¹ beingPreferably Hf or Zr and M² being Preferably Si or Al

The film deposited on the substrate in this example illustrates the casewherein a≠0, b≠0 and c=0.

All the information given in Example I are applicable in this ExampleIII, except that a M² metal source is additionally needed.

The M² containing precursor is also introduced into the reactor to cratethe M² source of metal. This M² containing precursor source shall bepreferably:

a) a silicon (or germanium) source and is selected from, but not limitedto, the group consisting of disiloxane, trisilylamine, disilane,trisilane, a alkoxysilane SiH_(x)(OR¹)_(4-x), a silanolSi(OH)_(x)(OR¹)_(4-x) (preferably Si(OH)(OR¹)₃; more preferablySi(OH)(OtBu)₃ an aminosilane SiH_(x)(NR¹R²)_(4-x) (where x is comprisedbetween 0 and 4; R¹ and R² are independently H or a C1-C6 carbon chain,either linear, branched or cyclic; preferably TriDMAS SiH(NMe₂)₃; BTBASSiH₂(NHtBu)₂) BDEAS SiH₂(NEt₂)₂) and mixtures thereof (or theirgermanium equivalent); orb) an aluminum source selected from the group comprisingtrimethylaluminum, dimethylaluminum hydride, an alkoxyalane AlR^(i)_(x)(OR′)_(3-x) (where x is comprised between 0 and 4; R¹ and R² areindependently H or a C1-C6 carbon chain, either linear, branched orcyclic; preferably AlR¹R²(OR′), most preferably AlMe₂(OiPr)), anamidoalane AlR^(i) _(x)(NR′R″)_(3-x) (where x is comprised between 0 and4; R¹ and R² are independently H or a C1-C6 carbon chain, either linear,branched or cyclic) and mixtures thereof; orc) a tantalum (or niobium) source selected from the group comprisingTa(OMe)₅, Ta(OEt)₅, Ta(OR¹)₄(O—C(R²)(R³)—CH₂—OR⁴) (each R^(i) isindependently H or a C1-C6 carbon chain, either linear, branched orcyclic, preferably TATDMAE Ta(OEt)(OCMe₂CH₂—OMe)),Ta(OR¹)₄(O—C(R²)(R³)—CH₂—N(R⁴)(R⁵)) (each R^(i) is independently H or aC1-C6 carbon chain, either linear, branched or cyclic, Ta(NMe₂)₅,Ta(NEt₂)₄, Ta(NEt₂)₅, Ta(═NR¹)(NR²R³)₃ (each R¹ and R² are independentlyH or a C1-C6 carbon chain, either linear, branched or cyclic and wherethe amino ligand can have different substituant) and mixtures thereof;or their niobium counterparts.d) a lanthanide metal source (Sc, Y, La, Ce, Pr, Nd, Gd . . . ) sourcewith at least one β-diketonate ligand, such as of the formLn(—O—C(R¹)—C(R²)—C(R³)—O—)(—O—C(R⁴)—C(R⁵)—C(R⁶)—O—)(—O—C(R⁷)—C(R⁸)—C(R⁹)—O—) where each R^(i) is independently H or a C1-C6 carbon chain, eitherlinear, branched or cyclic), or of the form of a cyclopentadienyllanthanide Ln(R¹Cp)(R²Cp)(R³CP) (where each R^(i) is independently H ora C1-C6 carbon chain, either linear, branched or cyclic),Ln(NR¹R²)(NR³R⁴)(NR⁵R⁶) (where each R^(i) is bonded to nitrogen and isindependently H or a C1-C6 carbon chain, either linear, branched orcyclic or an alkylsilyl chain of the form SiR⁷R⁸R⁹ where each R^(i) isbonded to silicon and is independently H or a C1-C4 carbon chain, eitherlinear, branched or cyclic)e) a IVA metal source with M² is similar or different from M¹ but inwhich the M² source is different from the M¹ metal source introduced instep b) in the reactor, said IVA metal source being selected from(R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z), M¹(OR¹)₄ or otheralkoxide-containing metal sources, M(NR¹R²)₄, or adducts containingthese species.f) a divalent metal (preferably Mg, Ca, Zn) selected from the groupcomprising metal β-diketonates or adducts containing these species.

The invention is directed to the deposition of dielectric films (formula(M¹ _(1-a) M² _(a)) O_(b) N_(c)) onto a support such as a wafer, in areactor using ALD, CVD, MOCVD, pulse CVD processes.

Example IV Deposition of M¹M² Metal Oxynitride Films with M¹ beingPreferably Hf or Zr and M² being Preferably Si or Al

The film deposited on the substrate in this example illustrates the casewherein a≠0, b≠0 and c≠0.

All the information given in Example III is applicable in this case,except that nitrogen needs to be introduced into the reactor.

The nitrogen source shall be selected from the group comprising nitrogen(N2), ammonia, hydrazine and alkyl derivatives, N-containing radicals(for instance N., NH., NH₂.), NO, N₂O, NO₂.

Example V Examples of New Group IV Precursors for Group IV MetalContaining Thin Film Deposition

Hf(iPrCp)₂H₂, Hf(nPrCp)₂H₂, Hf(EtCp)₂H₂, Hf(MeCp)₂Me₂, Hf(EtCp)₂Me₂,Hf(MeCp)₂EtMe, Hf(EtCp)₂EtMe, Hf(MeCp)₂nPrMe, Hf(MeCp)₂Et₂,Hf(MeCp)(EtCp)Me₂, Hf(MeCp)(EtCp)EtMe, Hf(iPrCp)₂EtMe, Hf(Me₂ Cp)₂Me₂,Hf(Et₂ Cp)₂Me₂, Hf(MeCp)(MeOp)Me₂, Hf(EtCp)(MeOp)Me₂, Hf(MeCp)(EtOp)Me₂,Hf(MeCp)(MeOp)EtMe, Hf(iPrOp)₂H₂, Hf(nPrOp)₂H₂, Hf(EtOp)₂H₂,Hf(MeOp)₂Me₂, Hf(EtOp)₂Me₂, Hf(MeOp)₂EtMe, Hf(EtOp)₂EtMe,Hf(MeOp)₂nPrMe, Hf(MeOp)₂Et₂, Hf(MeOp)(EtOp)Me₂, Hf(MeOp)(EtOp)EtMe,Hf(iPrOp)₂EtMe, Hf(Me₂Op)₂Me₂, Hf(Et₂Op)₂Me₂, Hf(C₅Me₅)₂Me₂,Hf(MeCp)₂Cl₂, Hf(EtCp)₂Cl₂, Hf(iPrCp)₂Cl₂, Hf(MeCp)(EtCp)Cl₂,HfCp(MeCp)Cl₂, Hf(MeOp)₂Cl₂, Hf(EtOp)₂Cl₂, Hf(iPrOp)₂Cl₂,Hf(MeOp)(EtOp)Cl₂, HfOp(MeOp)Cl₂, Zr(iPrCp)₂H₂, Zr(nPrCp)₂H₂,Zr(EtCp)₂H₂, Zr(MeCp)₂Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂EtMe, Zr(EtCp)₂EtMe,Zr(MeCp)₂nPrMe, Zr(MeCp)₂Et₂, Zr(MeCp)(EtCp)Me₂, Zr(MeCp)(EtCp)EtMe,Zr(iPrCp)₂EtMe, Zr(Me₂ Cp)₂Me₂, Zr(Et₂ Cp)₂Me₂, Zr(MeCp)(MeOp)Me₂,Zr(EtCp)(MeOp)Me₂, Zr(MeCp)(EtOp)Me₂, Zr(MeCp)(MeOp)EtMe, Zr(iPrOp)₂H₂,Zr(nPrOp)₂H₂, Zr(EtOp)₂H₂, Zr(MeOp)₂Me₂, Zr(EtOp)₂Me₂, Zr(MeOp)₂EtMe,Zr(EtOp)₂EtMe, Zr(MeOp)₂nPrMe, Zr(MeOp)₂Et₂, Zr(MeOp)(EtOp)Me₂,Zr(MeOp)(EtOp)EtMe, Zr(iPrOp)₂EtMe, Zr(Me₂Op)₂Me₂, Zr(Et₂Op)₂Me₂,Zr(C₅Me₅)₂Me₂, Zr(MeCp)₂Cl₂, Zr(EtCp)₂Cl₂, Zr(iPrCp)₂Cl₂,Zr(MeCp)(EtCp)Cl₂, ZrCp(MeCp)Cl₂, Zr(MeOp)₂Cl₂, Zr(EtOp)₂Cl₂,Zr(iPrOp)₂Cl₂, Zr(MeOp)(EtOp)Cl₂, ZrOp(MeOp)Cl₂, Ti(iPrCp)₂H₂,Ti(nPrCp)₂H₂, Ti(EtCp)₂H₂, Ti(MeCp)₂Me₂, Ti(EtCp)₂Me₂, Ti(MeCp)₂EtMe,Ti(EtCp)₂EtMe, Ti(MeCp)₂nPrMe, Ti(MeCp)₂Et₂, Ti(MeCp)(EtCp)Me₂,Ti(MeCp)(EtCp)EtMe, Ti(iPrCp)₂EtMe, Ti(Me₂ Cp)₂Me₂, Ti(Et₂ Cp)₂Me₂,Ti(MeCp)(MeOp)Me₂, Ti(EtCp)(MeOp)Me₂, Ti(MeCp)(EtOp)Me₂,Ti(MeCp)(MeOp)EtMe, Ti(iPrOp)₂H₂, Ti(nPrOp)₂H₂, Ti(EtOp)₂H₂,Ti(MeOp)₂Me₂, Ti(EtOp)₂Me₂, Ti(MeOp)₂EtMe, Ti(EtOp)₂EtMe,Ti(MeOp)₂nPrMe, Ti(MeOp)₂Et₂, Ti(MeOp)(EtOp)Me₂, Ti(MeOp)(EtOp)EtMe,Ti(iPrOp)₂EtMe, Ti(Me₂Op)₂Me₂, Ti(Et₂Op)₂Me₂, Ti(C₅Me₅)₂Me₂,Ti(MeCp)₂Cl₂, Ti(EtCp)₂Cl₂, Ti(iPrCp)₂Cl₂, Ti(MeCp)(EtCp)Cl₂,TiCp(MeCp)Cl₂, Ti(MeOp)₂Cl₂, Ti(EtOp)₂Cl₂, Ti(iPrOp)₂Cl₂,Ti(MeOp)(EtOp)Cl₂, TiOp(MeOp)Cl₂,

1-21. (canceled) 22: A method of forming on at least one support atleast one metal containing dielectric films having the formula (M¹_(1-a), a M² _(a)) O_(b) N_(c), wherein: 0≦a<1 0<b≦3, preferably1.5≦b≦2.5 0≦c≦1, preferably 0≦c≦0.5 M¹ and M² being metals said methodcomprising the steps of: (a) providing a substrate into a reactor; and(b) introducing into said reactor at least one metal containingprecursor having the formula:(R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z)  wherein: M¹=Hf, Zr and/or Ti;(R_(y)Op) represents one pentadienyl (Op) ligand, substituted or not,with y R substituents in any position on Op; (R_(t)Cp) represents onecyclopentadienyl (Cp) ligand, substituted or not, with t R substituentsin any position on Cp; Each R substituting the pentadienyl or Rsubstituting the cyclopentadienyl is a substituent independentlyselected from the group consisting of Cl, C1-C4 linear or branched,alkyl, alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl,each R substituting the pentadienyl or each R substituting thecyclopentadienyl being similar to or different from other R substitutingthe pentadienyl or other R substituting the cyclopentadienyl,respectively; Each R′ is a ligand independently selected from the groupconsisting of H, a halogen (F, Cl, Br, I), C1-C4 linear or branched,alkyl, alkylamides, alkoxide, alkylsilylamides, amidinates, carbonyl,each R′ being similar or different; x is an integer representing thenumber of pentadienyl (Op) ligand, substituted or not; z is an integerrepresenting the number of cyclopentadienyl (Cp) ligand, substituted ornot; y is an integer representing the number of substituents on each Op,and is independently selected for each Op; t is an integer representingthe number of substituents on each Cp, and is independently selected foreach Cp; 0≦x≦3, preferably x=0 or 1; 0≦z≦3, preferably z=2; 0≦y≦7,preferably y=2 and in this case each R is methyl; 0≦t≦5, preferably t=1and R is a methyl group; and Unspecified substituents to Op or Opligands are H by default; (c) optionally introducing at least one M²containing precursor, M² being selected from the group essentiallyconsisting of Mg, Ca, Zn, B, Al, In, Lanthanides (Sc, Y, La and otherrare earths), Si, Ge, Sn, Ti, Zr, Hf, V, Nb, Ta; (d) providing at leastone oxygen containing and/or nitrogen containing fluid into saidreactor; (e) reacting said at least one metal containing precursor withsaid at least one oxygen containing and/or nitrogen containing fluid;and (f) depositing said (M¹ _(1-a) M² _(a)) O_(b) N_(c) film onto saidsubstrate at a temperature comprised between 100 to 500° C., preferablybetween 150° C. and 350° C., provided that when a=0, b=2, c=0, x=0, z=2,at least one t on at least one Cp is different from zero. 23: The methodof claim 22, wherein the oxygen containing fluids are selected from thegroup consisting of O₂, 03, H₂O, H₂O₂, oxygen-containing radicals suchas O. or OH. and mixtures thereof. 24: The method of claim 22, whereinthe nitrogen-containing fluids are selected from the group consisting ofN₂, NH₃, hydrazine and its alkyl or aryl derivatives,nitrogen-containing radicals such as N., NH., NH₂. and mixtures thereof.25: The method of claim 22, wherein the oxygen and nitrogen-containingfluids are selected from the group consisting of NO, NO₂, N₂O, N₂O₅,N₂O₄ and mixtures thereof. 26: The method of claim 22, wherein thepressure is comprised between 1 Pa and 100000 Pa, preferably 25 Pa and1000 Pa. 27: The method of claim 22, wherein the various reactants canbe introduced simultaneously (chemical vapor deposition), sequentially(atomic layer deposition) or combinations of continuous and pulseintroduction of each precursor. 28: The method of claim 22, whereinfurther comprising the step of: (g) providing at least one metalcontaining precursor containing at least one of the followingprecursors: M¹(NMe₂)₄, M¹(NEt₂)₄, M¹(NMeEt)₄, M¹(mmp)₄, M¹(OtBu)₄,M¹(OtBu)₂(mmp)₂ and mixtures thereof. 29: The method of claim 22,wherein the at least one metal containing precursor introduced in stepb) has a melting point below 50 C, preferably below 35° C. 30: Themethod of claim 29, wherein the at least one metal containing precursoris liquid at room temperature. 31: The method of claim 22, furthercomprising the step of: (h) mixing together at least two different metalcontaining precursors A and B to provide a precursor mixture, A being(R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z), and B being selected from thegroup consisting of (R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z) M¹(NMe₂)₄,M¹(NEt₂)₄, M¹(NMeEt)₄, M¹(mmp)₄, M¹(OtBu)₄, M¹(OtBu)₂(mmp)₂ and mixturesthereof; and (i) providing said metal precursor mixture into saidreactor. 32: The method of claim 31 wherein step (h) and (i) are carriedout instead of step (b). 33: The method of claim 22, to form an M¹oxydecontaining film wherein a=0, b being equal to about 2 and c=0, the metalcontaining precursor of steps (b) and/or (h) being selected from thegroup consisting of: Hf(MeCp)₂Me₂, HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂,Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂, Zr(MeCp)₂Me₂, ZrCp(MeCp)Me₂,Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂ and mixtures thereof.34: The method of claim 22, to form an M¹oxynitride-containingdielectric film wherein a=0, 1.5≦b≦2.5 and 0<c≦0.5, the metal containingprecursor of step (b) and/or (h) being selected from the groupconsisting of HfCp₂Me₂, Hf(MeCp)₂Me₂, HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂,Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂, Zr(MeCp)₂Me₂, ZrCp(MeCp)Me₂,Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂, Zr(MeCp)₂(CO)₂. 35: The method of claim22, to form an M¹M² oxide containing dielectric film wherein 0≦a<1 andc=0, the metal containing precursor of step (b) and/or (h) beingselected from the group consisting of HfCp₂Me₂, Hf(MeCp)₂Me₂,HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂,Zr(MeCp)₂Me₂, ZrCp(MeCp)Me₂, Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂,Zr(MeCp)₂(CO)₂ the M² containing precursor of step (c) being introducedinto the reactor, said precursor being preferably selected from thegroup consisting of Si, Mg and/or Ta. 36: The method of claim 35,wherein the M² containing precursor is selected from the groupconsisting of disiloxane, trisilylamine, disilane, trisilane,alkoxysilane SiH_(x)(OR¹)_(4-x,) silanol Si(OH)_(x)(OR¹)_(4-x)(preferably Si(OH)(OR¹)₃; more preferably Si(OH)(OtBu)₃ aminosilaneSiH_(x)(NR¹R²)_(4-x) (where x is comprised between 0 and 4; R¹ and R²are independently selected from the group consisting of H or a C1-C6carbon chain, either linear, branched or cyclic; preferably TriDMASSiH(NMe₂)₃; BTBAS SiH₂(NHtBu)₂; BDEAS SiH₂(NEt₂)₂), (or their germaniumequivalent and mixtures thereof, trimethylaluminum, dimethylaluminumhydride, an alkoxyalane AlR^(i) _(x)(OR′)_(3-x) (where x is comprisedbetween 0 and 4; R¹ and R² are independently H or a C1-C6 carbon chain,either linear, branched or cyclic; preferably AlR¹R²(OR′), mostpreferably AlMe₂(OiPr)), amidoalane AlR^(i) _(x)(NR′R″)_(3-x) (where xis comprised between 0 and 4; R¹ and R² are independently H or a C1-C6carbon chain, either linear, branched or cyclic), Ta(OMe)₅, Ta(OEt)₅,Ta(OR¹)₄(O—C(R²)(R³)—CH₂—OR⁴) (each R^(i) is independently H or a C1-C6carbon chain, either linear, branched or cyclic, preferably TAT-DMAETa(OEt)(OCMe₂CH₂—OMe)), Ta(OR¹)₄(O—C(R²)(R³)—CH₂—N(R⁴)(R⁵)) (each R^(i)is independently H or a C1-C6 carbon chain, either linear, branched orcyclic, Ta(NMe₂)₅, Ta(NEt₂)₄, Ta(NEt₂)₅, Ta(═NR¹)(NR²R³)₃ (each R¹ andR² are independently H or a C1-C6 carbon chain, either linear, branchedor cyclic and where the amino ligand can have different substituent) andeach of their niobium counterparts, a lanthanide metal source (Sc, Y,La, Ce, Pr, Nd, Gd . . . ) source with at least one β-diketonate ligand,such as of the formLn(—O—C(R¹)—C(R²)—C(R³)—O—)(—O—C(R⁴)—C(R⁵)—C(R⁶)—O—)(—O—C(R⁷)—C(R⁸)—C(R⁹)—O—)where each R^(i) is independently H or a C1-C6 carbon chain, eitherlinear, branched or cyclic), or of the form of a cyclopentadienyllanthanide Ln(R¹Cp)(R²Cp)(R³Cp) (where each R^(i) is independently H ora C1-C6 carbon chain, either linear, branched or cyclic),Ln(NR¹R²)(NR³R⁴)(NR⁵R⁶) (where each R^(i) is bonded to nitrogen and isindependently H or a C1-C6 carbon chain, either linear, branched orcyclic or an alkylsilyl chain of the form SiR⁷R⁸R⁹ where each R^(i) isbonded to silicon and is independently H or a C1-C4 carbon chain, eitherlinear, branched or cyclic), a IVA metal source with M² is similar ordifferent from M¹ but in which the M² source is different from the M¹metal source introduced in step b) in the reactor, said IVA metal sourcebeing selected from (R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z), M¹(OR¹)₄ orother alkoxide-containing metal sources, M(NR¹R²)₄, or adductscontaining these species. a divalent metal A source (preferably Mg, Ca,Zn) of the form A(—O—C(R¹)—C(R²)—C(R³)—O—)(—O—C(R⁴)—C(R⁵)—C(R⁶)—O—)(where each R^(i) is independently H or a C1-C6 carbon chain, eitherlinear, branched or cyclic) or of the form of a cyclopentadienyllanthanide A(R¹Cp)(R²Cp) (where each R^(i) is independently H or a C1-C6carbon chain, either linear, branched or cyclic). 37: The method ofclaim 22, to form an M¹M² oxynitride containing dielectric film wherein0≦a<1 and 0<c≦0.5, the metal containing precursor of step (b) and/or (h)being selected from the group consisting of HfCp₂Me₂, Hf(MeCp)₂Me₂,HfCp(MeCp)Me₂, Hf(EtCp)(MeCp)Me₂, Hf(EtCp)₂Me₂, Hf(MeCp)₂(CO)₂,Zr(MeCp)₂Me₂, ZrCp(MeCp)Me₂, Zr(EtCp)(MeCp)Me₂, Zr(EtCp)₂Me₂,Zr(MeCp)₂(CO)₂, the M² containing precursor of step (c) being introducedinto the reactor, said precursor being preferably selected from thegroup consisting of Si, Mg and/or Ta, and wherein in step (d) at leastone oxygen containing precursor and at least one nitrogen containingprecursor is introduced into the reactor. 38: The method of claim 37,wherein the M² containing precursor is selected from the groupconsisting of disiloxane, trisilylamine, disilane, trisilane, aalkoxysilane SiH_(x)(OR¹)_(4-x), a silanol Si(OH)_(x)(OR¹)_(4-x)(preferably Si(OH)(OR¹)₃; more preferably Si(OH)(OtBu)₃ an aminosilaneSiH_(x)(NR¹R²)_(4-x) (where x is comprised between 0 and 4; R¹ and R²are independently H or a C1-C6 carbon chain, either linear, branched orcyclic; preferably TriDMAS SiH(NMe₂)₃; BTBAS SiH₂(NHtBu)₂); BDEASSiH₂(NEt₂)₂) and mixtures thereof (or their germanium equivalent),trimethylaluminum, dimethylaluminum hydride, an alkoxyalane AlR^(i)_(x)(OR′)_(3-x) (where x is comprised between 0 and 4; R¹ and R² areindependently H or a C1-C6 carbon chain, either linear, branched orcyclic; preferably AlR¹R²(OR′), most preferably AlMe₂(OiPr)), anamidoalane AlR^(i) _(x)(NR′R″)_(3-x) (where x is comprised between 0 and4; R¹ and R² are independently H or a C1-C6 carbon chain, either linear,branched or cyclic), Ta(OMe)₅, Ta(OEt)₅, Ta(OR¹)₄(O—C(R²)(R³)—CH₂—OR⁴)(each R^(i) is independently H or a C1-C6 carbon chain, either linear,branched or cyclic, preferably TAT-DMAE Ta(OEt)(OCMe₂CH₂—OMe)),Ta(OR¹)₄(O—C(R²)(R³)—CH₂—N(R⁴)(R⁵)) (each R^(i) is independently H or aC1-C6 carbon chain, either linear, branched or cyclic, Ta(NMe₂)₅,Ta(NEt₂)₄, Ta(NEt₂)₅, Ta(═NR¹)(NR²R³)₃ (each R¹ and R² are independentlyH or a C1-C6 carbon chain, either linear, branched or cyclic and wherethe amino ligand can have different substituent), and each of theirniobium counterparts, a lanthanide metal source (Sc, Y, La, Ce, Pr, Nd,Gd . . . ) source with at least one β-diketonate ligand, such as of theformLn(—O—C(R¹)—C(R²)—C(R³)—O—)(—O—C(R⁴)—C(R⁵)—C(R⁶)—O—)(—O—C(R⁷)—C(R⁸)—C(R⁹)—O—)where each R^(i) is independently H or a C1-C6 carbon chain, eitherlinear, branched or cyclic), or of the form of a cyclopentadienyllanthanide Ln(R¹Cp)(R²Cp)(R³Cp) (where each R^(i) is independently H ora C1-C6 carbon chain, either linear, branched or cyclic),Ln(NR¹R²)(NR³R⁴)(NR⁵R³) (where each R^(i) is bonded to nitrogen and isindependently H or a C1-C6 carbon chain, either linear, branched orcyclic or an alkylsilyl chain of the form SiR⁷R⁸R⁹ where each R^(i) isbonded to silicon and is independently H or a C1-C4 carbon chain, eitherlinear, branched or cyclic), a IVA metal source with M² is similar ordifferent from M¹ but in which the M² source is different from the M¹metal source introduced in step b) in the reactor, said IVA metal sourcebeing selected from (R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z), M¹(OR¹)₄ orother alkoxide-containing metal sources, M(NR¹R²)₄, or adductscontaining these species. a divalent metal A source (preferably Mg, Ca,Zn) of the form A(—O—C(R¹)—C(R²)—C(R³)—O—)(—O—C(R⁴)—C(R⁵)—C(R⁶)—O—)(where each R^(i) is independently H or a C1-C6 carbon chain, eitherlinear, branched or cyclic) or of the form of a cyclopentadienyllanthanide A(R¹Cp)(R²Cp) (where each R^(i) is independently H or a C1-C6carbon chain, either linear, branched or cyclic). 39: A new precursorcomprising composition for semi-conductor or RAM manufacture, saidprecursor having the formula;(R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z) wherein: M¹=Hf, Zr and/or Ti;(R_(y)Op) represents one pentadienyl (Op) ligand, substituted or not,with y R in any position on Op; (R_(t)Cp) represents onecyclopentadienyl (Cp) ligand, substituted or not, with t R in anyposition on Cp; Each R substituting the pentadienyl or R substitutingthe cyclopentadienyl are substituents independently selected from thegroup consisting of C1-C4 linear or branched, alkyl, alkylamides,alkoxide, alkylsilylamides, amidinates, carbonyl, each R substitutingthe pentadienyl or each R substituting the cyclopentadienyl beingsimilar to or different from other R substituting the pentadienyl orother R substituting the cyclopentadienyl, respectively; Each R′ is aligand independently selected from the group consisting of C1-C4 linearor branched, alkyl, alkylamides, alkoxide, alkylsilylamides, amidinates,carbonyl, each R′ being similar or different; x is an integerrepresenting the number of pentadienyl ligand, substituted or not; z isan integer representing the number of cyclopentadienyl ligand,substituted or not; y is an integer representing the number ofsubstituents on each Op, and is independent by selected for each Op; tis an integer representing the number of substituents on each Cp, and isindependent selected for each Cp; 0≦x≦3, preferably x=0 or 1; 0≦z≦3,preferably z=2; 0≦y≦7, preferably y=2 and in this case each R is methyl;0≦t≦5, preferably t=1 and R is a methyl group; Unspecified substituentsto Cp or Op ligands are H by default; and All R′ are not simultaneouslyequal to H when x=0, provided that when a=0, b=2, c=0, x=0, z=2, atleast one t on at least one Cp is different from zero. 40: The newprecursor comprising composition of claim 39, wherein it furthercomprises a second metal containing precursor, different from the firstmetal precursor, said second metal containing precursor being selectedfrom the group consisting of (R_(y)Op)_(x)(R_(t)Cp)_(z)M¹R′_(4-x-z),M¹(NMe₂)₄, M¹(NEt₂)₄, M¹(NMeEt)₄, M¹(mmp)₄, M¹ (OtBu)₄, M¹ (OtBu)₂(mmp)₂and mixtures thereof. 41: The new precursor composition of claim 39,wherein the precursor melting point is lower than or equal to 50° C.